Fungicides



ii jaw XE? :ZQQSMQM I 2,954,314 Patented Sept. 27, 1960 ea ns system, as for example sodium, potassium, calcium, bar- 2954314 ium, aluminum, lead, silver, copper, zinc, mercury, cerium, iron, nickel and also alkyl-mercury, alkoxyalkyl- FUNGICIDES mercury, aryl-mercury and halogen-mercur 5 The N-alkyland N-cycloalkyl-N-nitroso-hydroxylg fi gfgfi g fggg gffi g j ggg fifig zg gggg fi amines are suitable according to this invention for the Anifim & Soda Fabfik Akfiengeseuschaft, Ludwigs protection of substrates endangered by m urious fungi, hafen (Rhine), Germany such as cultivated plants, fruit, paper, textiles, glue,

u tanning liquors, leather, wood, mechanical wood pulp,

N0 Drawmg- Filed 1957: 679,150 synthetic substances or emulsions of synthetic substances,

Claims priority, application Germany Aug. 25, 1956 lacquers and the like. Depending on their solubility and purpose of use they may be used 1n known manner in.

6 Claimsaqueous solution or dispersion, dissolved in oil or as an oily solution emulsified in water, or in the form of This invention relates to a new fungicidal agent. 15. preparations, capable of being scattered or dusted, in

It is already known that saltsof N-aryl-N-m'trosohyadmixture with inert materials, such as talc, clay or droxylamines have fungicidal action. shale meal. Wetting agents, as for example alkyl or aryl We have found that N-nitroso-hydroxylamines nd th i sulfonates, and adhesives based on resins, wood ethers,

salts of the general formula waxes, or the like, may also be incorporated in the preparations.

7 R-N The fungicidal activity of the compounds is illustrated 1 1 in the following examples, but the invention is not limited V to these examples.

w in which R represents an aliphatic, .araliphatic or cyclo- EXAMPLE 1 G aliphatic radical and X hydrogen, a metal or an arm 25 monium radical, are excellent fungicides which are superior to the corresponding aryl-substituted compounds as regards their efifect and stability. As compared with the compounds of the aromatic series known frornthe US. patent specification No. 2,635,978, the fungicides accord- ;Eifig gj g g mventlon are also charactenzed by fungus was determined after incubation for 5 days at Highly active aliphatic and cycloaliphatic substituents In Table R are for example methyl, isopropyl, benzyl, butyl, cyclo indicates full fungus J- dense, Closed myhexyl, hydroxmethyl-cyclohexyl, cyano-cyclohexyl-, cyclo- 35 celium cover,

heptyl and cyclo-octyl radicals. As. the substituent X indicates slightly inhibited fungus growth; thin or Finely ground mixtures of talc with increasing amounts of active substance of the compositions specified in the table are dusted with the addition of spores of the mould fungus onto nutrient agar Aspergillus niger, 17 mg. of

30 each mixture of active substance, talc and spores being used for each square centimetre. The growth of-the there are suitable, besides hydrogen and ammonium, for loose mycelium cover, example alkyl-ammonium or cycloalkyl-ammonium, the indicates strongly inhibited fungus growth: only 150- monovalent or polyvalent metals of the 1st to 4th main lated small mycellum islands, and

groups and'the 1st to 8th sub-groups of the periodic 40 indicates total inhibition of the fungus growth.

Table 1.Gr0wth of Aspergillus niger When using RN-0--X Percentage content of active substance in the mixture of active substance and talc.

, NO in whlch- X= 0.075 0.15 0.31 0 ea 1.25 2 5 5 U isopr pyl eyc1ohexy1-ammonium 1%. rar e; 0 00 e y rogen y Do sodium potassiunm.-. V ammonium ca1cium p r 1)-, mercury chlonde (HgGl) zinc lead (II) cyclohexyl-ammoniumwn cerium (III) Do barium cycl0heptyl ammonium Do copper g1)... cyclo-octy ammonium Do copper (II) 'Doz c zyl--- ammonium. Do copper (11).-.- hyl copper (II). yet y -cyc c pper(11) exy For comparison ammonium 91 1 "T1",

Control without active substance 3 EXAMPLE 2 Leaves of grape vines in pots are sprayed with aqueous dispersions of a finely ground mixture of 80 parts by weight of the Copper salt of N cyclohexyl-N-nitrosohydroxylamine and N-isopropyl-N-nitrosohydroxylamine and 20 parts by weight of sodium lignin sulfonate. For comparison the corresponding mixture of the copper salt of N-phenyl-n-nitrosohydroxylamine is used. After the sprayed coating has dried, the underside of the leaves is infected by spraying on a spore suspension of grape vine fungus '(Plzzsmopara vitic'o'la). To intensify the infection conditions, the plants were 'then kept for 12 hours in a chamber saturated with water vapor at 20 C. After remaining for 8 days in 'the greenhouse at temperatures varying between 20 and 30 C. the plants are again placed in the said moist chamber for 12 hours to intensity the outbreak of spores. Counting the spore positions on the undersides of the leaves gave the following results.

Percent of attacked leaves after treatment with the copper salt ofat a concentration of the spraying solutionof N-cyclohexyl- N-isopropyl- N-phenyl- N-nitrosohy- N-nitrosohy- N-nitrosohydroxylamine droxylainine droxylamine Control 54 7 EXAMPLE 3 30 grams of finely grated orange peel are extracted for 2 hours with 120 grams of water. The filtrate is made up to 1 litre with water and 30 grams of agar added. After sterilisation at 100 (3., it is introduced in a flatlayer in 3 cos. batches into Petri dishes. To the 3 cos. of agar contained in each dish there is added 0.2 cc. of active substance solution or dispersion of the contents given in the following Table 2. Infection is carried out by dusting the surface of the agar with spores of green citrus mould (Penicillium italicum). After incubation for 8 days at 25 'C., the fungus growth given in Table 2 has taken place. In this table,

+++ indicates a luxuriant mycelium cover,

++ indicates a loose mycelium cover,

+ indicates only isolated small mycelium islands, and indicates no mycelium (total inhibition).

EXAMPLE 4 Oranges are dipped in solutions or dispersions of active substances of the contents given in Table 3. After the coating has dried, they are dusted with spores of green citrus mould and then stored in a moist chamber at 25 C. -to intensify the infection conditions. The attack of the fruit after 8 days is given in the table corresponding to the gradations:

+ =closed myceliumr cover, ++=loose mycellium cover, +1=isolated mycelium islands, ('+)=slight traces of mycelium and -=no mycelium (total inhibition).

Table 2.Gr0wlh of Penicillium italicum when using RNOX in which- Percentage of the active substance in the solution of the NO active substance ammonium calcium. copper; ammonium--- Comparison phenyl ammonium--. n y opner- Control without active substance addition Table 3.--Gr'0wth of Penicillium italicum \vhen u'siug R'N-*O-X in which-1 Percentage content of active substance in the active N O substance solution cyclohexyl ammonium Do... calcium... Do copper-.- cycl'o-octy ammonium.

Comparison phcnyl ammonium..-

Do. copper Control (fruit dipped in water with active substance) EXAMPLE 5 25% dilutions 'ofpolyvinyl pyrrolidone (K-value 30) have addedtothe'm fungicidal 'additions and are then kept for 8 weeks at 25 C. after inoculation with a mixture of mould fungus spores. The fungus growth was as shown in'Table 4 corresponding to the gradations:

++-=as without active substance, =isolated colonies, (+)=1 small colony, -l=total inhibition.

EXAMPLE 6 0.01% by weight of N-nitroso-N-cyclohexy1-hydroxylamine ammonium salt is added to a 20% aqueous solution of a copolymer of equal parts by Weight of acrylamide and methacrylamide. After storage for 3 months at room temperature, the sample is still without any fungus attack, whereas an untreated comparative sample becomes mouldy even after a short time.

EXAMPLE 7 A number of samples, each of grams of a liquid vegetable extract mixture with a 23% pure tanning agent content, consisting of 60 parts by weight of chestnut wood extract and 40 parts by weight of fir bark extract, are made up with water to 1 litre (this tanning solution approximately corresponds to one of the average liquors Table 4 When using- Fungus growth, mg. of active substance in batch N-nitroso-N-cyclohexyl-hydrox- 'ylamin'e ammonium'salt 'para-hydroxybenzoic acid-methyl ester-m;

Control-withoutactlve substance-++.

ble to mould) and 50 mg. of one of the following N- nitroso-N-cyclohexylhydroxylamine salts added: ammonium salt, cyclohexyl ammonium salt, zinc salt and calcium salt. All samples remain free from mould during an observation period of 3 weeks. A comparative sample without any addition exhibits strong fungus attack even after 5 days.

EXAMPLE 8 and exposed to putrefaction for 14 days at 30 C. When removed from the earth, the strips have changed as may be seen from Table 5.

Table 5 Prime ation gn Degree of destruction 1st bath, g. per litre 2d bath, g. per litre slightly discolored in N-nitroso-N cyclohexylplaces.

hydroxylamine ammonium salt.

20 copper acetate.

Do unchanged.

moderately attacked,

brittle. (control) total destruction.

We claim:

1. A fungicidal composition comprising as a highly active fungicidal ingredient a compound of a cation selected from the class consisting of hydrogen, ammonium, alky-l-substituted ammonium, sodium, potassium, calcium, barium, aluminum, lead, silver, copper,

nickel, and chloromercury,

RNO to 1 wherein R is a member selected from the class consisting of alkyl, cycloalkyl and aralkyl radicals having from 1 to 8 carbon atoms and the same radicals containing one substituent selected from the class consisting of hydroxymethyl and cyano groups, and an inert carrier for said active ingredient.

2. A fungicidal composition as claimed in claim 1 wherein R is cyclohexyl.

3. A fungicidal composition comprising as a highly active fungicidal ingredient an inorganic salt of the anion RN 0 to 1 wherein R is a member selected fir'om the class consisting of alkyl, cycloalkyl and aralkyl radicals having from 1 to 8 carbon atoms and the same radicals containing one substituent selected from the class consisting of hydroxymethyl and cyano groups, and an inert carrier for said active ingredient.

4. A fungicidal composition as claimed in claim 3 wherein R is cyclohexyl.

5. A fungicidal composition as claimed in claim 3 zinc, mercury, cerium, iron, and the anion wherein the highly active fungicidal ingredient is a copper salt of N-isopropyl-N-nitrosohydroxylamine.

6. A fungicidal composition as claimed in claim 3 wherein the highly active fungicidal ingredient is the cupric salt of N-methyl-N-nitrosohydroxylamine.

References Cited in the file of this patent UNITED STATES PATENTS 2,635,978 Massengale Apr. 21, 1953 

1. A FUNGICIDAL COMPOSITION COMPRISING AS A HIGHLY ACTIVE FUNGICIDAL INGREDIENT A COMPOUND OF A CATION SELECTED FROM THE CLASS CONSISTING OF HYDROGEN, AMMONIUM, ALKYL-SUBSTITUTED AMMONIUM, SODIUM, POTASSIUM, CALCIUM, BARIUM, ALUMINUM, LEAD, SILVER, COPPER, ZINC, MERCURY, CERIUM, IRON, NICKEL, AND CHLOROMERCURY, AND THE ANION 